Compositions containing cyclopentadiene adducts and the use thereof for chemically stable coatings

ABSTRACT

Composition comprising (a) at least one component selected from phenolic resins, amino resins, polyfunctional isocyanates and derivatives thereof, and (b) at least one cyclopentadiene adduct as an additional component obtainable by reacting at least one unsaturated ester product with an optionally substituted cyclopentadiene, wherein the unsaturated ester product is obtainable by reacting an alcohol component, comprising a mono- or polyhydric alcohol, with a carboxylic acid component comprising a mono- or polybasic carboxylic acid or a derivative thereof, with the proviso that the mono- or polyhydric alcohol and/or the mono- or polybasic carboxylic acid comprise at least one non-aromatic double bond and with the proviso that the mono- or polyhydric alcohol is polyhydric and/or the mono- or polybasic carboxylic acid is polybasic, wherein the component (b) comprises functional groups (B) which can enter into a chemical bond with the functional groups (A) of component (a).

The invention relates to compositions containing at least onecyclopentadiene adduct and at least one further component selected fromphenolic resins, amino resins, polyfunctional isocyanates andderivatives thereof, as well as coating compositions containing thesecompositions as binders. The resulting coatings exhibit a high degree ofchemical resistance; the coating compositions are therefore suitable asepoxide-free packing lacquers.

The invention furthermore relates to coated articles, particularlycontainers whose coating can be obtained by applying the coatingcomposition of the present invention.

Coatings with a high degree of chemical resistance are in high demand,among other things for the coating of packaging materials that come intocontact with aggressive media. What are referred to as packing lacquersare lacquers for packaging materials made from plastic materials,aluminum and sheet metal, which impart decorative properties to thesecontainers and protect them from their contents; such lacquers are forexample used for coating the inside of containers made from tinplate,black plate, chrome-plated steel sheet (TFS=tin-free steel) and sheetaluminum. The containers can for example be tin cans, soda cans,containers for pharmaceuticals (e.g. tubes), aerosol cans, drums andbarrels. The interior coating has to exhibit a high degree of chemicalresistance (since it is in contact with the contents of the container);depending on the type of packaging it may have to be resistant tosterilization, and in addition, it has to be highly elastic (beexpandable and allow flanging) for the manufacture and sealing of thecontainers. Epoxide-/phenol-based lacquers, which are also referred toas “gold varnishes” due to their self-yellowing during baking, arefrequently used, as are pigmented white finishes on the basis ofepoxide/melamine resins or polyester/melamine resins.

The reasons why lacquers on the basis of epoxide/phenol are so commonlyused are the outstanding properties of these coatings with respect totheir processability (paintability, formability), their excellentsensory properties (tasteless and odorless) and the above-mentionedresistance to aggressive media.

It is, however, a considerable drawback that low-molecular components ofan epoxide resin based e.g. on bisphenol A are endocrine and can migratefrom the coating into the contents of the container; thus, if thecontent is food, they can end up in the human body.

The effects of endocrine substances have for example been identified infish—particularly in the run-off of water treatment plants whereelevated concentrations of endocrine substances are present. Atheoretical adverse effect on human reproductiveness is being discussed.

Replacing these resins with less controversial ones while maintainingtheir positive properties would therefore be desirable.

As is the case with acrylates, polyester resins in combination withmelamine resins are preferably used in lacquers for coating the exteriorof containers since their chemical stability is generally insufficient.

Most of the time, the few systems on the basis of polyester phenolicresins which could be considered suitable for interior coating and arecommercially available contain polyesters with a very high molecularweight and therefore typically have a rather low solids content of 40 to60% according to DIN 55671 at a viscosity of 2,000 to 7,000 mPa·s at 25°C. according to DIN 53015, which in the end results in a high price anda high VOC content; at the same time they do not even completely fulfillindustry requirements with respect to their resistance properties.

Practical applications demand that container coatings, in particularinterior coatings of food containers, exhibit good adhesion, e.g. on thesheet metal used for the container, as well as high resistance tochemicals and sterilization, do not affect taste, smell or appearance ofthe contents, and have suitable mechanical properties with respect toflexibility and hardness.

Food packaging also has to comply with the regulations of the Food andDrug Administration (FDA) and the U.S. Department of Agriculture (USDA),or the corresponding regulations in other countries (e.g. BGA[Bundesgesundheitsamt, the German Health Department], VGB [the DutchFood and Health Protection Directorate], Synoptic Document of theScientific Committee on Food of the Commission of the EuropeanCommunities, Resolution AP 96(5) of the Council of Europe).

It is therefore the object of the present invention to providecompositions that are free of epoxides and lead to coatings havingexcellent mechanical properties and chemical resistance whichfurthermore do not comprise any endocrine components.

Other objects of the present invention are the provision of coatingcompositions and coated articles, in particular containers, that aresuitable for packaging food, whereby the coating compositions leave opena certain latitude regarding the drying parameters, show sufficientstorage stability and can be applied by means of conventionalapplication devices.

The objects of the invention are achieved by a composition comprising

-   -   (a) at least one component selected from phenolic resins, amino        resins, polyfunctional isocyanates and derivatives thereof, and    -   (b) at least one cyclopentadiene adduct as an additional        component obtainable by reacting at least one unsaturated ester        product with an optionally substituted cyclopentadiene, wherein        the unsaturated ester product is obtainable by reacting an        alcohol component, comprising a mono- or polyhydric alcohol,        with a carboxylic acid component comprising a mono- or polybasic        carboxylic acid or a derivative thereof, with the proviso that        the mono- or polyhydric alcohol and/or the mono- or polybasic        carboxylic acid comprise at least one non-aromatic double bond        and with the proviso that the mono- or polyhydric alcohol has to        be polyhydric and/or the mono- or polybasic carboxylic acid has        to be polybasic,    -   wherein the component (b) comprises functional groups (B) which        can enter into a chemical bond with the functional groups (A) of        component (a),    -   or a coating composition comprising    -   (a) the above composition    -   (b) at least one solvent and    -   (c) optionally at least one additional component selected from        fillers, dyes, pigments and additives such as fungicides,        bactericides, drying agents, antiskinning agents, hardening        accelerators, flow improvers, emulsifiers, wetting agents,        antiflotation agents, antisettling agents and matting agents.

The individual components of the compositions containing cyclopentadieneadducts of the present invention and the coating compositions of thepresent invention are described in more detail below.

In the following, the term “coating composition” is used in the sense ofthe term “coating substance” known in the art; the coating substance(coating composition) provides the coating of an article by way ofapplication, drying and optionally baking.

The ester products modified with cyclopentadiene are hereinafter alsoreferred to as cyclopentadiene adducts.

Unless indicated otherwise, the following definitions apply in thepresent specification: An alkyl group comprises straight-chain andbranched hydrocarbon groups with preferably 1 to 20 carbon atoms,especially preferred 1 to 12 carbon atoms; optionally, one or moresubstituents can be present (preferably one to three) which areindependently selected from halogen atoms, OH, SH and NH₂.

Halogen atoms are fluorine, chlorine, bromine and iodine atoms.

An aromatic hydrocarbon group or aryl group as referred to in thefollowing is preferably an aromatic structural unit with 6 to 20 carbonatoms (especially preferred 6 to 12 carbon atoms) optionally comprisingone or more substituents (preferably 1 to 3) selected from OH, SH, NH₂,halogen atoms and C₁-C₁₂ alkyl groups. Examples include optionallysubstituted phenyl and naphthyl groups.

An aliphatic hydrocarbon group is a saturated or unsaturated hydrocarbongroup which can be straight-chain or branched and preferably comprises 1to 30 carbon atoms (especially preferred 1 to 20 carbon atoms). Thealiphatic hydrocarbon group can optionally be substituted with one ormore substituents (preferably 1 to 3) independently selected from OH,SH, NH₂ and halogen atoms.

A cycloaliphatic hydrocarbon group is a saturated or unsaturated(non-aromatic) hydrocarbon group which preferably comprises 3 to 8carbon atoms (especially preferred 5 to 6 carbon atoms). Thecycloaliphatic hydrocarbon group can optionally be substituted with oneor more substituents (preferably 1 to 3) independently selected from OH,SH, NH₂ and halogen atoms and C₁-C₁₂ alkyl groups.

The term “acid derivatives” as used in the following refers to acidanhydrides, acid amides, acid halides and esters, e.g. with aliphatic orcycloaliphatic alcohols or C₇-C₂₀-aralkyl-OH, wherein in the case ofesters, C₁-C₁₈ alkyl esters are preferred and C₁-C₆ alkyl esters areespecially preferred.

As a first essential component (component (a)), the compositions of thepresent invention comprise at least one component selected from phenolicresins, amino resins, polyfunctional isocyanates and derivativesthereof, having functional groups (A).

All phenolic resins obtained by the condensation of phenols and carbonylcompounds (e.g. aldehydes such as formaldehyde), the derivatization ofthe resulting condensate, or the addition of phenols to unsaturatedcompounds such as e.g. acetyls, terpenes, or natural resins can be usedas component (a) of the compositions according to the present invention.Preferred examples include phenol, butylphenol, nonylphenol, cresol,xylenol and bisphenol A resins and derivatives thereof; resols areespecially preferred. If necessary, they can be modified in mannersknown to the person skilled in the art in order to increase theircompatibility with the cyclopentadiene adduct; possible modificationsinclude for example etherifications (particularly butylations). Apreferred manner of hydrophobing is an etherification of the phenolicresins by introducing hydrophobic groups such as e.g. butyl groups.

Typical commercially available resins which can be used after suitablesolvents have been selected taking into account the different polarityof the two components of the composition of the present invention arefor example Uravar FB 209 BT-57 (DSM Resins B.V.), Askofen R 9500(Ashland-Südchemie-Kernfest GmbH), and GPRI 7550 (Georgia PacificResins, Inc.).

In addition to phenolic resins, amino resins can also be used ascomponent (a), i.e. polycondensation products of carbonyl compounds (inparticular formaldehyde, but also higher aldehydes and ketones) andcompounds containing NH groups (e.g. urea, melamine, urethane, cyanamideand dicyanamide, aromatic amines and sulfonamides). Preferred aminoresins are melamine and benzoguanamine resins and derivatives thereof,such as e.g. etherified resins (in particular butylated resins) whichhave the great advantage of being very compatible with other componentsof coating compositions in general and the cyclopentadiene adducts usedas component (b) in particular.

Commercially available resins that can be used in the present inventionin combination with the cyclopentadiene adducts include e.g. Cymel 303(Cytec Netherlands (CRP) B.V.) and Cymel 5011 (Cytec Netherlands (CRP)B.V.).

In addition to phenolic resins and amino resins, polyfunctionalisocyanates, in the following also referred to as polyisocyanates, canbe used as component (a) as well.

Aliphatic, cycloaliphatic, aromatic and heterocyclic isocyanates with atleast two isocyanate groups in one molecule can be used aspolyisocyanates. In addition to monomers, oligomers or prepolymers canbe used as well. Examples include toluene-2,4-diisocyanate,toluene-2,6-diisocyanate, 3-phenyl-2-ethylene diisocyanate,1,5-naphthalene diisocyanate, cumene-2,4-diisocyanate,4-methoxy-1,3-diphenyl diisocyanate, 4-chloro-1,3-phenyl diisocyanate,diphenylmethane-4,4′-diisocyanate, diphenylmethane-2,4′-diisocyanate,diphenylmethane-2,2′-diisocyanate, 4-bromo-1,3-phenyl diisocyanate,4-ethoxy-1,3-phenyl diisocyanate, 2,4′-diisocyanate diphenylether,5,6-dimethyl-1,3-phenyl diisocyanate, 2,4-dimethyl-1,3-phenyldiisocyanate, 4,4-diisocyanatodiphenylether, 4,6-dimethyl-1,3-phenyldiisocyanate, 9,10-anthracene diisocyanate, 2,4,6-toluene triisocyanate,2,4,4′-triisocyanatodiphenylether, 1,4-tetramethylene diisocyanate,1,6-hexamethylene diisocyanate, 1,10-decamethylene diisocyanate,1,3-cyclohexylene diisocyanate, 4,4′-methylen-bis(cyclohexylisocyanate),xylene diisocyanate,1-isocyanato-3-methylisocyanato-3,5,5-trimethylcyclohexane (isophoronediisocyanate), 1,3-bis(isocyanato-1-methylethyl)benzene (m-TMXDI), and1,4-bis(isocyanate-1-methylethyl)benzene (p-TMXDI).

Blocked polyisocyanates such as e.g. the commercially available UradurYB147 S1 (DSM Resins B.V.) and DESMODUR BL 3175 (BAYER AG) can be usedas well.

As another essential component, the compositions of the presentinvention comprise at least one cyclopentadiene adduct obtainable byreacting at least one unsaturated ester product and an optionallysubstituted cyclopentadiene. The ester product in turn is obtainable byreacting an alcohol component, comprising a mono- or polyhydric alcohol,with a carboxylic acid component comprising a mono- or polybasiccarboxylic acid. In this reaction, it is important that the mono- orpolyhydric alcohol and/or the mono- or polybasic carboxylic acidcomprise at least one non-aromatic double bond. Furthermore, the mono-or polyhydric alcohol has to be polyhydric and/or the mono- or polybasiccarboxylic acid has to be polybasic.

The resulting cyclopentadiene adduct has to comprise functional groups(B) capable of entering into a chemical bond with the functional groups(A) of the other essential component described above (component (a)).

The cyclopentadiene adducts are obtainable by reacting at least oneunsaturated ester product and cyclopentadiene at elevated temperatures(e.g. a temperature of 200 to 300° C., more preferred 240 to 280° C.,especially preferred 250 to 280° C.) in a closed system under pressure(e.g. an excess pressure of 0.2 to 15 bar, more preferred an excesspressure of 1 to 10 bar and especially preferred an excess pressure of 3to 8 bar) whereby an inert solvent can be used. Usually,dicyclopentadiene (optionally substituted) is used for this reactionwhich, however, breaks down into cyclopentadiene at a temperature of 170to 180° C. The cyclopentadiene or dicyclopentadiene can optionallycomprise one or more substituents independently selected from halogens(fluorine, chlorine, bromine and iodine) and C₁-C₆ alkyl groups. Due tomore difficult hydrolysis, these rather low-viscosity—compared with thepolyesters mentioned above—cyclopentadiene adducts which have a solidscontent of more than 70% e.g. in white spirit, measured according to DIN55671, at a viscosity of about 500 to 3,500 mPa·s (measured at 25° C.according to DIN 53015) have an excellent chemical resistance.

The reactivity of the cyclopentadiene adduct is controlled by the numberof functional groups (B) of the cyclopentadiene adducts, i.e. in the endby varying characteristics such as e.g. the hydroxyl number or the acidnumber.

In addition to hydroxyl groups, basically all nucleophilic groups thatcan cause chemical cross-linking by reacting with the methylol groups ofphenolic resins, amino groups of amino resins, such as e.g. melamineresins or benzoguanamine resins or the isocyanate groups orpolyfunctional isocyanates can be functional groups, e.g. the amino orthiol group as well.

A desired side effect of the functional group (B) present in thecyclopentadiene adduct is the reduction of hydrophobicity, which isparticularly necessary if phenolic resins are used as a second componentsince otherwise incompatibilities could ensue in the composition and/orthe coating itself.

Cyclopentadiene adducts especially suitable for use in the presentinvention are e.g. those containing 5 to 60 wt.-% of cyclopentadienebased on the entire adduct in general, preferably 20 to 50 wt.-% andespecially preferred 35 to 50 wt.-%. According to a preferredembodiment, the hydroxyl content of the cyclopentadiene adducts ispreferably 0.1 wt.-% to 20 wt.-% OH based on the cyclopentadiene adduct,especially preferred 0.5 to 10%, and particularly preferred 1 to 8%.

Naturally, cyclopentadiene adducts are advantageously soluble innon-polar solvents, however, due to the functional groups present in theadducts, which can for example be quantified by characteristics such asthe hydroxyl number or acid number, they are to a certain degree alsostable in solution in a more polar medium.

For the preparation of the ester product, an alcohol component,comprising a mono- or polyhydric alcohol, and a carboxylic acidcomponent, comprising a mono- or polybasic carboxylic acid, or aderivative thereof are used. For this purpose, the mono- or polyhydricalcohol and the mono- or polybasic carboxylic acid have to be selectedsuch that at least one of them is “polyvalent” and at least one of themcomprises at least one non-aromatic double bond.

Furthermore, the functional groups (B) are usually introduced into thecyclopentadiene adduct by preparing the unsaturated ester productaccordingly, i.e. the alcohol and acid components are selectedappropriately. According to a preferred embodiment, a mono- orpolyhydric saturated alcohol and a mono- or polybasic unsaturatedcarboxylic acid with preferably 1 to 6 non-aromatic double bonds permolecule are used.

It is furthermore preferred that the alcohol component comprise apolyhydric alcohol, and it is then especially preferred that thecarboxylic acid component comprise a monobasic carboxylic acid.Polyhydric alcohols with 2 to 6 hydroxyl groups per molecule areparticularly preferred.

Mixtures of mono- and/or polyhydric alcohols and/or mixtures of mono-and/or polybasic carboxylic acids or derivatives thereof can be used aswell, as long as the prerequisites regarding functionality andnon-aromatic double bond are met. It is also possible that one or moreof the used alcohols and/or one or more of the used carboxylic acids arepresent in esterified form. The esterified alcohols and carboxylic acidsare preferably triglycerides, but other esters are possible as well.

Examples of suitable mono- or polyhydric alcohols include

-   -   monohydric alcohols of the general formula R⁰—OH, wherein R⁰ is        a saturated or unsaturated monovalent aliphatic or        cycloaliphatic hydrocarbon group, wherein an aliphatic or        cycloaliphatic hydrocarbon group optionally comprises one or        more ether oxygen atoms and optionally comprises one or more        substituents independently selected from halogen atoms, NH₂ and        SH,    -   dihydric alcohols of the general formula HO—R¹—OH, wherein R¹ is        a divalent saturated or unsaturated aliphatic or cycloaliphatic        hydrocarbon group, which optionally comprises one or more        substituents (e.g. 1 to 3) independently selected from halogen,        NH₂ and SH, the hydrocarbon group can comprise one or more        (preferably no more than four) ether oxygen atoms and preferably        comprises two to thirty, especially preferred two to twenty,        carbon atoms. The dihydric alcohols are preferably saturated. R¹        is preferably selected from aliphatic C₂-C₁₀ hydrocarbon groups.        Examples of such dihydric alcohols include ethylene glycol,        diethylene glycol, propylene glycol, dipropylene glycol,        butylene glycol, dibutylene glycol and neopentyl glycol,    -   polyhydric alcohols of the general formula        HO(CH₂)_(n)—CH₂—CR²OH(CH₂)_(m)—CH₂—(CH₂)_(p)OH    -    wherein n, m and p are independently 0, 1, 2 or 3, and R² is a        hydrogen atom, a saturated or unsaturated aliphatic or        cycloaliphatic hydrocarbon group with preferably 1 to 12 carbon        atoms or a group HO(CH₂)_(q)—, wherein q=0, 1, 2 or 3. The        hydrocarbon group can optionally comprise one or more (e.g. 1        to 3) substituents independently selected from halogen, NH₂ and        SH. Examples of such polyhydric alcohols include glycerin,        trimethylolethane, trimethylolpropane and pentaerythritol,    -   other polyhydric alcohols such as threitol, erythritol,        arabitol, adonitol, xylitol, dipentaerythritol, sorbitol,        mannitol and dulcitol, wherein the alcohols optionally comprise        one or more substituents independently selected from halogen        atoms, SH and NH₂, and    -   polyhydric alcohols with aromatic rings of the formula        R⁵—(R⁶—OH)_(k), wherein R⁵ is an aromatic hydrocarbon group such        as e.g. phenyl or naphthyl which, in addition to k substituents        of the formula —(R⁶—OH), optionally comprises one or more        additional substituents independently selected from halogen        atoms, C₁-C₁₂ alkyl groups, NH₂ and SH, and wherein R⁶ is a        saturated or unsaturated aliphatic hydrocarbon group with 1 to        12 carbon atoms and the unit —(R⁶—OH) is bonded to the aromatic        1 to 4 times (i.e. k is an integer from 1 to 4); examples of        such alcohols include benzyl alcohol, dimethyloibenzene and        trimethylolbenzene.

The mono- or polyhydric alcohol used in the present invention canoptionally comprise one or more functional groups selected from SH andNH₂.

Of course, mixtures of mono- or polyhydric alcohols as e.g. mentionedabove can be used as well; one or more alcohols can optionally bepresent in esterified form.

Aliphatic and cycloaliphatic saturated and unsaturated C₂-C₃₀ alcohols(more preferably C₂-C₂₀) as well as C₆-C₃₀ alcohols having aromaticstructural units are preferred as mono- or polyhydric alcohols.According to one embodiment, the alcohol component comprises a mono- orpolyhydric alcohol without a double bond. According to anotherembodiment, the alcohol component comprises a polyhydric alcohol.Alcohols having two to six hydroxyl groups per molecule are preferred.It is preferred that saturated polyhydric alcohols be used.

According to one embodiment, the alcohol component consists of a mixtureof polyhydric alcohols, one or more of which can be present inesterified form; the alcohols can be esterified with saturated and/orunsaturated carboxylic acids with 1 to 20 carbon atoms and 0 to 6non-aromatic double bonds.

For preparing the unsaturated ester product, a composition is preferablyused wherein the amount of the alcohol component accounts for about 10to 40 wt.-%, based on the sum of all components used.

The carboxylic acid component can comprise saturated and/or unsaturatedaliphatic and/or cycloaliphatic and/or aromatic monocarboxylic acids.They can be used individually or in admixture. Furthermore, mixtures ofmonocarboxylic acids and polybasic carboxylic acids can be used.

Suitable monocarboxylic acids or also suitable derivatives thereof arefor example those of the general formula R³—COOH, wherein R³ is an arylgroup optionally substituted with one or more straight-chain or branchedalkyl groups with preferably 6 to 10 carbon atoms or a straight-chain orbranched saturated or unsaturated aliphatic or cycloaliphatichydrocarbon group with preferably a total of 4 to 30 carbon atoms,especially preferred 10 to 20 carbon atoms, and optionally one or moresubstituents independently selected from halogen atoms, NH₂, SH and OH.

Typical examples of saturated carboxylic acids include isodecanoic acid,isooctanoic acid, cyclohexanoic acid and longer-chain carboxylic acids,as well as naturally occurring saturated fatty acids. Palmitic acid andstearic acid are examples of naturally occurring saturated carboxylicacids. However, modifications of natural unsaturated fatty or oleicacids that have been completely hydrogenated technologically aresuitable too.

Palmitoleic acid, oleic acid, erucic acid, ricinoleic acid, linoleicacid, linolenic acid, elaeostearic acid, arachidonic acid, clupanodonicacid, docosahexaenoic acid and mixtures thereof can for example be usedas unsaturated acids.

Monocarboxylic acids which in addition to the carboxy group comprise ahalogen atom, a hydroxyl group, amino group and/or thiol group, as isfor example the case in ricinoleic fatty acid, dimethylolpropionic acidor hydrolyzed, epoxidized fatty acids, have to be taken intoconsideration as well.

Benzoic acid and p-tert.-butylbenzoic acid are typical examples ofaromatic carboxylic acids.

Apart from that, the monocarboxylic acids for the preparation of theunsaturated ester product can either be used in the form of the freeacid, or amides, halides or anhydrides thereof, or in the form ofesters, e.g. with C₁-C₁₈ alkyl alcohols.

Suitable polycarboxylic acids are for example dicarboxylic acids of thegeneral formula HOOC—R⁴—COOH, wherein R⁴ is a divalent group selectedfrom a saturated or unsaturated branched or straight-chain aliphatic orcycloaliphatic group with 0 to 30 carbon atoms (preferably two to sixcarbon atoms) and an aromatic hydrocarbon group with preferably a totalof 6 to 30 carbon atoms optionally substituted with one or more C₁-C₆alkyl groups. These dicarboxylic acids as well can optionally compriseone or more functional groups selected from hydroxyl groups, aminogroups and thiol groups.

Examples include maleic acid, oxalic acid, malonic acid, fumaric acid,succinic acid, terephthalic acid, isophthalic acid, adipic acid,glutaric acid, azelaic acid and o-phthalic acid.

However, polycarboxylic acids of higher functionality, i.e.polycarboxylic acids with more than two (yet preferably no more thansix) carboxy groups per molecule, can be used as well.

Examples of polycarboxylic acids of higher functionality includetricarboxylic acids such as trimellitic acid, tricarballylic acid,trimesic acid or hemimellitic acid, tetracarboxylic acids such aspyromellitic acid, or polycarboxylic acids with more than four carboxygroups such as mellitic acid.

Acids which additionally comprise one or more OH groups, amino groups orthiol groups, such as malic acid, tartaric acid, mesotartaric acid,racemic acid or citric acid can also be used as polycarboxylic acids.

For the preparation of the unsaturated ester product, the mono-, di- andpolycarboxylic acids can either be used in the form of free acids, or asamides, halides or anhydrides thereof, or in the form of esters (e.g. ofstraight-chain or branched aliphatic C₁-C₁₈, more preferred C₁-C₆, orcycloaliphatic alcohols, or aralkyl-OH such as e.g. C₆-C₂₀).

According to a preferred embodiment, the unsaturated ester product usedfor the preparation of the cyclopentadiene adduct is an ester productthat is obtainable by reacting an alcohol component comprising apolyhydric saturated or unsaturated alcohol with preferably 2 to 6hydroxyl groups per molecule with a carboxylic acid component comprisingat least 3 wt.-% of long-chain unsaturated acids with 8 to 30 carbonatoms and 1 to 6 non-aromatic double bonds per molecule or derivativesthereof.

The carboxylic acid component used in this embodiment comprises at least3 wt.-%, preferably at least 20 wt.-%, especially preferred at least 40wt.-%, of long-chain unsaturated acids with 8 to 30 carbon atoms(preferably 10 to 24, especially preferred 14 to 20 carbon atoms) and 1to 6 non-aromatic double bonds (preferably 1 to 4) per molecule, orderivatives thereof such as amides, halides, anhydrides and esters, e.g.C₁-C₁₈ alkyl esters. Suitable long-chain unsaturated acids are forexample palmitoleic acid, oleic acid, erucic acid, ricinoleic acid,linoleic acid, linolenic acid, elaeostearic acid, arachidonic acid,clupanodonic acid, docosahexaenoic acid and mixtures thereof.

According to an even more preferred embodiment, the unsaturated esterproduct can be obtained by reacting a drying, semidrying or non-dryingoil and a polyhydric alcohol different from glycerin and optionally oneor more carboxylic acids (or carboxylic acid derivatives different fromtriglycerides). The terms drying/semidrying/non-drying oils refer tofatty oils containing unsaturated fatty acids as triglyceride. Whenexposed to atmospheric oxygen, the (semi)drying oils dry or undergooxidative curing to form solid, viscoplastic films. The drying capacitydepends on the proportion of unsaturated fatty acids in the oil as wellas on the number and position of the double bonds; it can be quantifiedon the basis of the iodine number which for drying oils is generallyabout>170, and for semidrying oils generally between about 100 and 170.The (semi)drying/non-drying oil is preferably linseed oil, soy oil,sunflower oil, safflower oil, rapeseed oil, cottonseed oil, tall oil,fish oil such as herring oil and whale oil, colza oil, tung oil,dehydrated castor oil, perilla oil, poppyseed oil, nut oil, hempseedoil, whale oil, beechnut oil, corn oil, sesame oil, peanut oil, castoroil, coconut oil, olive oil, palm oil, palm kernel oil, beef tallow,mutton tallow, lard, butter fat or a mixture thereof.

According to one embodiment, a composition is used for the preparationof the unsaturated ester product wherein the amount of monocarboxylicacids is preferably 30 to 95 wt.-%, more preferred 50 to 80 wt.-%, basedon the sum of all components used (i.e. alcohols and carboxylic acids).

Due to its unsaturated nature, the preparation of the unsaturated esterproduct is carried out at lower temperatures than for alkyd resins(usually between 150 and 250° C.) and preferably in the presence of aninert gas (such as e.g. nitrogen or argon) since the reaction ofatmospheric oxygen with the double bonds could cause discoloration oreven gelatinization.

As is common in resin chemistry, the resulting reaction water is removedby means of azeotropic distillation or with the help of a vacuum.

The stoichiometric ratios are adjusted in a manner known to the personskilled in the art such that unsaturated ester products with acidnumbers of preferably 0 to 40 mg KOH/g polymer, especially preferred 1to 20, and hydroxyl contents of preferably 0.1 to 20 wt.-%, morepreferred 0.5 to 10 wt.-%, and particularly preferred 1 to 8 wt.-% OH,based on unsaturated ester product.

The hydroxyl content is for example determined with acetic acidanhydride according to DIN 53240 or ISO 4629. The acid number ismeasured according to DIN 53402 or ISO 3682.

The compositions containing cyclopentadiene adducts according to thepresent invention can be used as binders for coating compositions andare especially suitable for packing lacquers. In addition to solventsand the binder on the basis of cyclopentadiene adduct/phenolic or aminoresin or polyisocyanate, the coating composition of the presentinvention can comprise common additional constituents such as dyes,pigments (metal pigments as well as inorganic, organic andorganometallic pigments), fillers (e.g. heavy spar, chalk, kaolin etc.)and additives; additives include e.g. fungicides, bactericides, dryingagents (e.g. heavy-metal salts of carboxylic acids such as cobaltoctoate or lead naphthenate soluble in the binders), antiskinning agents(antioxidants), hardening accelerators (e.g. p-toluene sulfonic acid,phosphoric acid or dodecylbenzene sulfonic acid), flow improvers (e.g.silicone-based), emulsifiers, wetting agents and antiflotation agents(e.g. cationic and non-ionic tensides, silicone oils, aluminum salts offatty acids or highly disperse silicic acids), wax-based lubricants,antisettling agents and matting agents (e.g. kieselguhr, talcum,synthetically obtained highly disperse silicic acids and polyolefinwaxes). It goes without saying that the coating of food containersprepared from the coating composition of the present invention shouldnot contain any harmful substances in order to avoid health hazards. Asolvent or solvent mixture is another component of the coatingcompositions according to the present invention. Examples includehydrocarbons (such as white spirit and xylene), alcohols, e.g. n- oriso-butanol, esters such as e.g. butyl acetate, etherified esters suchas methoxybutyl acetate, and ketones such as cyclohexanone.

The coating composition of the present invention preferably comprises 10to 90 wt.-% of the binder composition of the present invention based onthe total weight of the composition, more preferred 30 to 80 wt.-%.Preferably, 0.05 to 10 parts by weight of the second component (i.e.phenolic resin, amino resin, polyisocyanate), more preferred 0.1 to 1parts by weight, are used per part by weight of cyclopentadiene adduct.The additional components different from solvents are preferably presentin a total amount of 0 to 60 wt.-% of the composition, especiallypreferred 0 to 30 wt.-%.

The preparation of pigmented and unpigmented coating compositions iscarried out according to a process comprising the following steps:

-   -   (a) providing at least one component selected from phenolic        resins, amino resins, polyfunctional isocyanates and derivatives        thereof, said component comprising functional groups (A),    -   (b) preparing an unsaturated ester product as described above,    -   (c) reacting the unsaturated ester product obtained in step (b)        with an optionally substituted cyclopentadiene at room        temperature or an elevated temperature resulting in a        cyclopentadiene adduct comprising functional groups (B) which        can enter into a chemical bond with the functional groups (A) of        component (a),    -   (d) mixing the cyclopentadiene adduct obtained in step (c) with        at least one reactant according to (a),        and optionally    -   (e) mixing the mixture obtained in step (d) with at least one        solvent and optionally one or more additional components        selected from dyes, pigments, fillers and additives, whereby one        or more components and/or solvents can also already be added to        the component provided in step (a) and/or to the cyclopentadiene        adduct obtained in step (c).

The preparation of the coating composition comprising thecyclopentadiene adduct of the present invention is carried out by mixingsuitable reactants (step (d), above) at room temperature or an elevatedtemperature, preferably at 60 to 80° C. If the mixing is carried out atelevated temperatures, i.e. if a preliminary reaction takes placebetween the cyclopentadiene adduct and the suitable reactants, theproperties of the corresponding coating may be improved.

Common devices are used for mixing. According to one embodiment, it isalso possible to mix the cyclopentadiene adduct (component (b)) and/orthe reactant (component (a)) with one or more additional componentsand/or solvents before the two components are mixed in step (d).Depending on whether additional components and/or solvents are requiredor not, step (e) is either necessary or can be left out.

Suitable solvents for the coating compositions include e.g. alcoholssuch as n-butanol and iso-butanol, esters and etherified esters such as3-methoxy-n-butyl acetate and butyldiglycol acetate, aliphatichydrocarbons such as white spirit and special boiling-point gasoline140/165, aromatic hydrocarbons such as diisopropyinaphthalene andmixtures of aromatic hydrocarbons such as Hisol 10® and Hisol 15®. Thesolvent or solvent mixture best suited for specific components caneasily be determined by the person skilled in the art.

The binding compositions comprising at least one component (a) and atleast one component (b) usually have a solids content of 2 to 100%,preferably 55 to 85% and are characterized by excellent storagestability when phenolic resins, amino resins or blocked polyisocyanatesare used. The coating compositions can be prepared therefrom by adding(additional) solvent(s) and/or additional components. When unblockedpolyfunctional isocyanates are used it is preferred, due to theirreactivity, that the mixing with the cyclopentadiene adduct does nottake place until immediately prior to the application of the coatingcomposition to the article to be coated.

The coating composition of the present invention can be applied tocardboard, wood, glass, plastic materials, as well as metal and metalalloys. It is preferably used for coating metal surfaces such astinplate, black plate, TFS and sheet aluminum; adhesion is especiallygood on these surfaces. The coating compositions of the presentinvention are suitable both as primers and topcoats. The comply with theguidelines of the Food and Drug Administration (FDA) and the U.S.Department of Agriculture (USDA), leave open a certain latituderegarding the drying parameters and show a high storage stability.

The coating compositions of the present invention can be applied bymeans of conventional equipment; they can for example be sprayed orpoured onto the material to be coated, applied with rollers or a doctorblade, or using a dip coating process. The manner of coating is notparticularly restricted. Coil-coating and flat sheet coating should bementioned as particularly suitable coating processes.

In the case of coating compositions according to the present inventioncomprising phenolic resins, amino resins and/or blocked polyisocyanates,the coating is preferably baked after drying (if the material to becoated allows baking); this is preferably done at about 170° C. to 220°C. and for a time period of about 5 to 30 minutes. If the compositioncomprises free polyisocyanates, baking is usually not necessary.

A clear and highly lustrous coating with a layer thickness of preferably2 to 50 μm, more preferred 2 to 20 μm, and particularly preferred 4 to10 μm, is obtained.

The present invention also relates to articles, in particular containerssuch as cans, barrels and tanks, having a coating that was prepared byapplying the coating composition of the present invention, drying andoptionally baking. When preparing containers e.g. from metal it ispossible to first form the container and then coat the material or toapply the coating prior to forming. The coating compositions of thepresent invention are suitable for coating the outside of containers,but due to their chemical resistance, they can also be used for interiorcoatings.

In addition to containers, other articles such as e.g. crown caps, topsfor sealing jars etc., pipes, wires, heat exchangers etc. can also becoated with the coating compositions of the present invention.

The coated articles of the present invention are characterized by ahigh-gloss clear coating with good adhesion, scratch resistance, a highdegree of resistance to chemicals and sterilization; furthermore, in thecase of containers, the coating does not affect the taste, smell orappearance of the contents as e.g. foodstuffs. The coatings also exhibitsuitable mechanical properties with respect to flexibility and hardness.

The present invention also relates to a kit comprising two containers,wherein the first container comprises component (a) and the secondcontainer comprises component (b). In addition, the kit can optionallycomprise at least one solvent and/or further components selected fromdyes, pigments, fillers and additives, wherein the solvent and/or theadditional components can be present in one or more additionalcontainers and/or in the first and/or second container.

The invention will be explained in more detail in the followingexamples; however, they shall not restrict the invention in any way.

EXAMPLES Example 1

Preparation of Cyclopentadiene Adducts, in ParticularCyclopentadiene-modified Copolymer Resins on the Basis of Drying andSemidrying Oils

Copolymer Resin A

An unsaturated ester product was prepared at 220 to 240° C. in a mannerknown to the person skilled in the art in connection with polyester oralkyd resins from 21.20 kg soy oil, 4.00 g lithium hydroxide and 0.75 kgpentaerythritol and 0.61 kg phthalic acid anhydride using azeotropicdistillation; distillation was carried out until an acid number below 12was reached. The thus prepared unsaturated ester product was thenreacted with 17.30 kg dicyclopentadiene in a pressure-proof reactionvessel at 260 to 280° C., whereby the pressure temporarily reached about6 bar excess pressure.

The mixture was kept under pressure and at that temperature until 60.00g of a sample of the reaction mixture mixed with 40.00 white spiritreached a viscosity of 2,000 mPa·s at 25° C. measured according to DIN53015.

When this viscosity was reached, the reaction was terminated by coolingand reducing the reaction pressure to normal pressure.

While it was still warm, the resin was diluted with 13.50 kg whitespirit and then had a solids content of 74.2% (measured according to DIN55671) and a viscosity of 3,100 mPa·s at 25° C. (measured according toDIN 53015).

Copolymer Resin B

An unsaturated ester product was prepared—as described above forcopolymer resin A—from 20.80 kg linseed oil, 4.00 g lithium hydroxide,1.78 kg pentaerythritol and 1.43 kg phthalic acid anhydride. Thisunsaturated ester product was then reacted with 12.60 kgdicyclopentadiene, as described above. The reaction was terminated whena mixture of 70.00 g resin sample and 30.00 g white spirit had aviscosity of 1,000 mPa·s (at 25° C.). The resin was diluted with 12.50kg white spirit which resulted in a solids content according to DIN55671 of 75.1% and a viscosity of 1,640 mPa·s (at 25° C.) according toDIN 53015.

Example 2

Preparation of Coating Compositions

2.1. Coating Composition on the Basis of Copolymer Resin A and PhenolicResin

At room temperature, a solution of 0.65 kg amine-blockeddodecylbenzenesulfonic acid in a mixture of 1.12 kg isopropanol, 0.13 kgwater and 13.20 kg diisopropyinaphthalene was added under stirring to27.00 kg copolymer resin A; then 12.30 kg commercially availablephenolic resin A were added. The mixture was diluted with 10.00 kg3-methoxy-n-butyl acetate, which resulted in a clear 40% solution withhigh storage stability.

2.2. Coating Composition on the Basis of Copolymer Resin B and PhenolicResin

As described in 2.1., 27.00 kg copolymer resin B were mixed with 0.50 kgamine-blocked dodecylbenzenesulfonic acid, 1.30 kg isopropyl alcohol,0.13 kg water, 12.00 kg diisopropyinaphthalene and 13.10 kg phenolicresin B (60% butylated phenolic resin dissolved in n-butanol, molarratio formaldehyde to phenol=2.5) (60% butylated cresol resin dissolvedin n-butanol, molar ratio formaldehyde to cresol=2.5) and diluted with10.00 kg 3-methoxy-n-butyl acetate. A clear, storage-stable 41% solutionwas obtained.

2.3. Coating Composition on the Basis of Copolymer Resin A and AmineResin

Analogously to 2.1., 40.00 kg copolymer resin A were mixed with 0.22 kgamine-blocked dodecylbenzenesulfonic acid, 0.60 kg isopropyl alcohol,0.06 kg water, 8.00 kg diisopropylnaphthalene and 3.28 kg amine resin A(solvent-free HMMM resin) and diluted with 3.70 kgdiisopropyinaphthalene. A clear, storage-stable 60% solution wasobtained.

2.4. Coating Composition on the Basis of Copolymer Resin A and a Mixtureof a Phenolic Resin and Amine Resin

Analogously to 2.1., 32.00 kg copolymer resin A were mixed with 0.52 kgamine-blocked dodecylbenzenesulfonic acid, 1.35 kg isopropyl alcohol,0.14 kg water, 14.78 kg diisopropylnaphthalene, 11.27 kg phenolic resinA and 0.68 kg amine resin B (77% butylated benzoguanamine resindissolved in n-butanol) and diluted with 11.85 kg 3-methoxy-n-butylacetate. A clear, storage-stable 60% solution was obtained.

2.5. Coating Composition on the Basis of Copolymer Resin A and a Mixtureof Phenolic Resin and an Isocyanate Resin

Analogously to 2.1., 27.00 kg copolymer resin A were mixed with 0.65 kgamine-blocked dodecylbenzenesulfonic acid, 1.12 kg isopropanol, 0.13 kgwater, 13.20 kg diisopropylnaphthalene, 11.00 kg phenolic resin A and1.70 kg isocyanate resin (75% blocked aromatic product dissolved inHisol 10® and having an isocyanate content according to DIN 53185 of9.6%) and diluted with 10.00 kg 3-methoxy-n-butyl acetate, resulting ina clear 40% solution with high storage stability.

Upon three months of storage at room temperature, the thus producedlacquers showed no signs of change such as phase separation,precipitation or clouding. The properties of coatings prepared from thelacquers that had been stored for three months were in no way inferiorin quality compared to coatings prepared from fresh lacquer.

Example 3

Application and Drying of the Coating Compositions Prepared according toExample 2 on Tinplate

The lacquers were applied onto tinplate by means of 25 μm doctor bladesand baked for 15 minutes at 200° C. A golden, clear, scratch-resistantand highly lustrous coating with a layer thickness of 4 to 6 μm wasobtained. The coatings showed very good adhesion (Gt=TT=0) and a highresistance to acetone (>100 doublerubs) both before and after havingbeen subjected for 30 minutes at 130° C. to distilled water, 3% aceticacid, 3% sodium chloride solution and 2% urea solution, which caused nochange in the appearance of the coatings. Furthermore, the coatings metthe industry standards regarding hardness and flexibility.

Positive results were obtained both in practically oriented testmethods, such as the sudden bending stress test with a flexural impacttester or the production of cylindrical cups in an Erichsen cuppingtesting machine, as well as in practical applications such as theproduction of fish cans or can tops where no crack formation ordelamination was observed; the results were at least equally good as,and in some cases superior to, the test results of commerciallyavailable and established packing lacquers containing epoxide resins.

1. A composition comprising (a) at least one component selected fromphenolic resins, amino resins, polyfunctional isocyanates andderivatives thereof, and (b) at least one cyclopentadiene adduct as anadditional component obtainable by reacting at least one unsaturatedester product with an optionally substituted cyclopentadiene, whereinthe unsaturated ester product is obtainable by reacting an alcoholcomponent, comprising a mono- or polyhydric alcohol, with a carboxylicacid component comprising a mono- or polybasic carboxylic acid or aderivative thereof, with the proviso that the mono- or polyhydricalcohol and/or the mono- or polybasic carboxylic acid comprise at leastone non-aromatic double bond and with the proviso that the mono- orpolyhydric alcohol is polyhydric and/or the mono- or polybasiccarboxylic acid is polybasic, wherein the component (b) comprisesfunctional groups (B) which can enter into a chemical bond with thefunctional groups (A) of component (a).
 2. A composition according toclaim 1, wherein the mono- or polyhydric alcohol does not comprise anon-aromatic double bond and the mono- or polybasic carboxylic acid or aderivative thereof comprises at least one non-aromatic double bond.
 3. Acomposition according to claim 1, wherein the alcohol componentcomprises a polyhydric alcohol.
 4. A component according to claim 3,wherein the carboxylic acid component comprises a monobasic carboxylicacid or a derivative thereof and the alcohol component comprises apolyhydric alcohol.
 5. A composition according to claim 3, wherein thepolyhydric alcohol comprises two to six hydroxyl groups per molecule. 6.A composition according to claim 1, wherein the unsaturated esterproduct is obtainable by reacting an alcohol component comprising apolyhydric alcohol with a carboxylic acid component comprising at least3 wt.-% of long-chain unsaturated acids with 8 to 30 carbon atoms and 1to 6 non-aromatic double bonds or derivatives thereof.
 7. A compositionaccording to claim 1, wherein the mono- or polyhydric alcohol isselected from: (a) monohydric alcohols of the general formula R⁰—OH,wherein R⁰ is a saturated or unsaturated monovalent aliphatic orcycloaliphatic hydrocarbon group, wherein the aliphatic orcycloaliphatic hydrocarbon group optionally comprises one or more etheroxygen atoms and optionally comprises one or more substituentsindependently selected from a halogen atom, NH₂ and SH, (b) dihydricalcohols of the general formula HO—R¹—OH, wherein R¹ is a divalentsaturated or unsaturated aliphatic or cycloaliphatic hydrocarbon group,which optionally comprises one or more ether oxygen atoms and optionallycomprises one or more substituents independently selected from halogenatoms, SH and NH₂, (c) polyhydric alcohols of the general formulaHO(CH₂)_(n)—CH₂—CR²OH(CH₂)_(m)—CH₂—(CH₂)_(p)OH  wherein n, m and p areindependently 0, 1, 2 or 3, and R² is a hydrogen atom, a monovalentsaturated or unsaturated aliphatic or cycloaliphatic hydrocarbon groupor a group HO(CH₂)_(q)—, wherein q=0, 1, 2 or 3, wherein the aliphaticor cycloaliphatic hydrocarbon group optionally comprises one or moresubstituents independently selected from halogen atoms, NH₂ and SH, (d)the group of polyhydric alcohols consisting of threitol, erythritol,arabitol, adonitol, xylitol, pentaerythritol, sorbitol, mannitol anddulcitol, wherein the alcohols optionally comprise one or moresubstituents selected from SH, a halogen atom and NH₂, and (e)polyhydric alcohols with aromatic rings of the formula R⁵—(R⁶—OH)_(k),wherein R⁵ is an aromatic hydrocarbon group which, in addition to ksubstituents of the formula —(R⁶—OH), optionally comprises one or moreadditional substituents independently selected from halogen atoms,C₁-C₁₂ alkyl groups, NH₂ and SH, and wherein R⁶ can be the same ordifferent and represents a divalent saturated or unsaturated aliphatichydrocarbon group with 1 to 12 carbon atoms and k is an integer from 1to
 4. 8. A composition according to claim 3, wherein the polyhydricalcohol is saturated.
 9. A composition according to claim 1, wherein thealcohol component consists of a mixture of mono- and/or polyhydricalcohols, one or several of which can optionally be present inesterified form.
 10. A composition according to claim 1, wherein thecarboxylic acid component consists of a mixture of mono- and/orpolybasic carboxylic acids, one or several of which can optionally bepresent in esterified form.
 11. A composition according to claim 6,wherein the unsaturated ester product is obtained by reacting a drying,semidrying or non-drying oil and a polyhydric alcohol and optionally oneor more carboxylic acids or carboxylic acid derivatives different fromtriglycerides.
 12. A composition according to claim 11, wherein thepolyhydric alcohol is not glycerin.
 13. A composition according to claim6, wherein the carboxylic acid component comprises linseed oil, soy oil,sunflower oil, safflower oil, rapeseed oil, cottonseed oil, tall oil,fish oil, colza oil, tung oil, dehydrated castor oil, perilla oil,poppyseed oil, nut oil, hempseed oil, whale oil, beechnut oil, corn oil,sesame oil, peanut oil, castor oil, coconut oil, olive oil, palm oil,palm kernel oil, beef tallow, mutton tallow, lard, butter fat or amixture thereof.
 14. A composition according to claim 1, wherein thecarboxylic acid component comprises at least one carboxylic acid or aderivative thereof selected from: (a) monocarboxylic acids of thegeneral formulaR³—COOH  wherein R³ is an aryl group optionally substituted with one ormore straight-chain and branched alkyl groups or a straight-chain orbranched aliphatic or cycloaliphatic saturated or unsaturatedhydrocarbon group with optionally one or more substituents selected fromhalogen atoms, NH₂, SH and OH, (b) dicarboxylic acids of the generalformulaHOOC-R⁴—COOH  wherein R⁴ is a divalent group selected from a branched orstraight-chain aliphatic or cycloaliphatic saturated or unsaturatedgroup with 0 to 30 carbon atoms and an aromatic hydrocarbon groupoptionally substituted with one or more C₁-C₆ alkyl groups, (c)polycarboxylic acids selected from trimellitic acid, tricarballylicacid, trimesic acid, hemimellitic acid, pyromellitic acid and melliticacid, and (d) the group of carboxylic acids consisting of ricinenicacid, sorbic acid, acrylic acid, methacrylic acid and crotonic acid,wherein one or more of the carboxy groups are optionally not present ina free form, but as an acid amide, acid halide, anhydride or ester andwherein the at least one carboxylic acid optionally comprises one ormore functional groups selected from hydroxyl groups, thiol groups oramino groups.
 15. A composition according to claim 6, wherein thelong-chain unsaturated acid is selected from palmitoleic acid, oleicacid, erucic acid, ricinoleic acid, linoleic acid, linolenic acid,elaeostearic acid, arachidonic acid, clupanodonic acid, docosahexaenoicacid and mixtures thereof.
 16. A composition according to claim 1,wherein the optionally substituted cyclopentadiene is used in the formof the dicyclopentadiene optionally substituted correspondingly andobtained therefrom in situ.
 17. A coating composition comprising: (a) acomposition according to claim 1 (b) at least one solvent and (c)optionally an additional component selected from dyes, pigments,fillers, additives and mixtures thereof.
 18. A coating compositionaccording to claim 17, wherein the amount of the composition (a)accounts for 10 to 90 wt.-% based on the coating composition.
 19. Amethod of formulating a lacquer, comprising a) providing a compositionaccording to claim 1; and b) diluting said composition to apredetermined solids content to provide a lacquer.
 20. The method ofclaim 19, wherein the lacquer is a packing lacquer.
 21. A method ofcoating articles, comprising applying a coating composition according toclaim 17 to an article to be coated.
 22. The method of claim 21, whereinthe article is a metal article.
 23. An article comprising a coating,said coating having been obtained by applying a coating compositionaccording to claim 17, drying, and optionally baking.
 24. An articleaccording to claim 23, wherein the article is a container.
 25. Anarticle according to claim 24, wherein the container is a can, a barrelor a tank.
 26. An article according to claim 23, wherein the article isa metal article.
 27. An article according to claim 24, wherein thecoating is present at least on the inside of the container.
 28. Aprocess for coating a substrate selected from metal, plastic materials,glass, cardboard or wood, comprising applying a coating compositionaccording to claim 17 to the substrate, and drying, the coating on thesubstrate.
 29. A process according to claim 28, wherein the metal istinplate, black plate, TFS or sheet aluminum.
 30. A process according toclaim 29, wherein the coating composition is only applied to one side ofthe plate.
 31. A process for manufacturing containers comprising (a)coating a plate on at least one side according to the process of claim29, (b) forming containers from the coated plate obtained in step (a).32. A process for manufacturing containers comprising (a) forming thecontainer from metal, a plastic material, glass, cardboard or wood (b)coating the inside and/or the outside of the container obtained in step(a) according to the process of claim
 28. 33. A process for preparing acoating composition according to claim 17 comprising (a) providing atleast one component selected from phenolic resins, amino resins,polyfunctional isocyanates and derivatives thereof, said componentcomprising functional groups (A), (b) preparing an unsaturated esterproduct as described in any of claim 1, (c) reacting the unsaturatedester product obtained in step (b) with an optionally substitutedcyclopentadiene at room temperature or an elevated temperature resultingin a cyclopentadiene adduct comprising functional groups (B) which canenter into a chemical bond with the functional groups (A) of component(a), (d) mixing the cyclopentadiene adduct obtained in step (c) with atleast one reactant according to (a), and optionally (e) mixing themixture obtained in step (d) with at least one solvent and optionallyone or more additional components selected from dyes, pigments, fillersand additives, whereby one or more components and/or solvents can alsoalready be added to the component provided in step (a) and/or to thecyclopentadiene adduct obtained in step (c) before the componentprovided in step (a) and the cyclopentadiene adduct obtained in step (c)are brought into contact.
 34. A process according to claim 33, whereinthe optionally substituted cyclopentadiene is used in the form of thedicyclopentadiene optionally substituted correspondingly and obtainedtherefrom in situ.
 35. A kit comprising (i) a first container comprisingat least one component (a) selected from phenolic resins, amino resins,polyfunctional isocyanates and derivatives thereof, wherein thecomponent (a) comprises functional groups (A), and (ii) a secondcontainer comprising at least one cyclopentadiene adduct obtainable fromthe reaction as described in claim 1 and which comprises functionalgroups (B) which can enter into a chemical bond with the functionalgroups (A) of the component of the first container.
 36. A kit accordingto claim 35, further comprising at least one solvent and optionally oneor more components selected from dyes, pigments, fillers and additives,wherein the solvent and/or the additional components are present in thefirst and/or second container and/or in one or more additionalcontainers.
 37. A process according to claim 28, further comprising thestep of baking the coating on the substrate.